JP4668394B2 - Polyester resin composition - Google Patents

Description

（式中、−Ａ−は、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂-、−ＣＯ−、炭素数１〜２０のアルキレン基、または炭素数６〜２０のアルキリデン基であり、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、およびＲ⁸は、いずれも水素原子、ハロゲン原子、または炭素数１〜５の１価の炭化水素基であり、Ｒ⁹、Ｒ¹⁰はいずれも炭素数１〜５の２価の炭化水素基であり、Ｒ¹¹、Ｒ¹²はいずれも水素原子、炭素数１〜２０の１価の炭化水素基であり、それらはそれぞれ同一であっても異なっていても良い。ｍおよびｎはオキシアルキレン単位の繰り返し単位数を示し、２≦ｍ＋ｎ≦５０である。）
で表されるものが層状化合物の分散性および熱安定性の点から好ましい。
【００３４】
ポリエーテル化合物の使用量は、層状化合物と熱可塑性ポリエステル樹脂との親和性、ポリエステル樹脂組成物中での層状化合物の分散性が十分に高まるように調製し得る。必要であるならば、異種の官能基を有する複数種のポリエーテル化合物を併用し得る。従って、ポリエーテル化合物の使用量は一概に数値で限定されるものではないが、層状化合物１００重量部に対するポリエーテル化合物の配合量の下限値は、０．１重量部であり、好ましくは０．２重量部であり、より好ましくは０．３重量部であり、更に好ましくは０．４重量部であり、特に好ましくは０．５重量部である。層状化合物１００重量部に対する層状化合物の配合量の上限値は、２００重量部であり、好ましくは１８０重量部であり、より好ましくは１６０重量部であり、更に好ましくは１４０重量部であり、特に好ましくは１２０重量部である。ポリエーテル化合物量の下限値が０．１重量部未満であると層状化合物の微分散化効果が充分でなくなる傾向がある。また、ポリエーテル化合物量の２００重量部以上では効果が変わらないので、２００重量部より多く使用する必要はない。
【００３５】
層状化合物とポリエーテル化合物を混合する方法は特に限定されず、層状化合物とポリエーテル化合物を直接混合する方法や、水あるいは水を含有する極性溶媒中で層状化合物とポリエーテル化合物を混合する方法が挙げられる。混合の効率の点から、後者が望ましい。本発明において、ポリエーテル化合物で層状化合物を処理する方法は特に限定されず例えば、以下に示した方法で行い得る。
【００３６】
まず、層状化合物と分散媒を撹拌混合する。前記分散媒とは水または水を含有する極性溶媒を意図する。具体的には既に上述しているのでここでは省略する。
【００３７】
層状化合物と分散媒との攪拌の方法は特に限定されず、例えば、従来公知の湿式撹拌機を用いて行われる。該湿式撹拌機としては、撹拌翼が高速回転して撹拌する高速撹拌機、高剪断速度がかかっているローターとステーター間の間隙で試料を湿式粉砕する湿式ミル類、硬質媒体を利用した機械的湿式粉砕機類、ジェットノズルなどで試料を高速度で衝突させる湿式衝突粉砕機類、超音波を用いる湿式超音波粉砕機などを挙げることができる。より効率的に混合したい場合は、撹拌の回転数を１０００ｒｐｍ以上、好ましくは１５００ｒｐｍ以上、より好ましくは２０００ｒｐｍ以上にするか、あるいは５００（１／ｓ）以上、好ましくは１０００（１／ｓ）以上、より好ましくは１５００（１／ｓ）以上の剪断速度を加える。回転数の上限値は約２５０００ｒｐｍであり、剪断速度の上限値は約５０００００（１／ｓ）である。上限値よりも大きい値で撹拌を行ったり、剪断を加えてもそれ以上変わらない傾向があるため、上限値よりも大きい値で撹拌を行う必要はない。また、混合に要する時間は１〜１０分以上である。次いで、ポリエーテル化合物を加えてから同様の条件で更に撹拌を続け、十分に混合する。混合時の温度は室温で充分だが、必要に応じて加温しても良い。加温時の最高温度は用いるポリエーテル化合物の分解温度未満であり、かつ分散媒の沸点未満で有れば任意に設定されうる。その後、乾燥して必要に応じて粉体化する。
【００３８】
本発明のポリエステル樹脂組成物において、熱可塑性ポリエステル樹脂１００重量部に対するポリエーテル化合物で処理された層状化合物の配合量の下限値は、代表的には０．１重量部であり、好ましくは０．３重量部であり、より好ましくは０．５重量部であり、さらに好ましくは１．０重量部であり、特に好ましくは１．５重量部である。配合量の上限値は、代表的には１５０重量部であり、好ましくは１００重量部であり、より好ましくは７０重量部であり、更に好ましくは５０重量部であり、特に好ましくは３０重量部となるように調製される。層状化合物の配合量の下限値が０．１重量部未満であると機械的特性の向上、反りの低減などの改善効果が不充分となる場合があり、上限値が１５０重量部を超えると成形体の表面外観が損なわれる傾向がある。
【００３９】
また、層状化合物に由来するポリエステル樹脂組成物の灰分率の下限値は、代表的には０．１重量％であり、好ましくは０．３重量％であり、より好ましくは０．５重量％であり、さらに好ましくは１．０重量％であり、特に好ましくは１．５重量％と成るように調製され、灰分率の上限値は、６０重量％であり、好ましくは５０重量％であり、より好ましくは４０重量％であり、更に好ましくは３０重量％と成るように調製される。灰分率の下限値が０．１重量％未満であると機械的特性の向上、反りの低減などの改善効果が不充分となる場合があり、上限値が６０重量％を超えると成形体の表面外観が損なわれる傾向がある。
【００４０】
本発明のポリエステル樹脂組成物中で分散している層状化合物の構造は、使用前の層状化合物が有していたような、層が多数積層したμｍサイズの凝集構造とは全く異なる。すなわち、ポリエーテル化合物で処理される事によって、層同士が劈開し、互いに独立して細分化する。その結果、層状化合物はポリエステル樹脂組成物中で非常に細かく互いに独立した薄板状で分散し、その数は、使用前の層状化合物に比べて著しく増大する。この様な薄板状の層状化合物の分散状態は以下に述べる等価面積円直径［Ｄ］、アスペクト比（層長さ／層厚の比率）、分散粒子数、最大層厚及び平均層厚で表現され得る。
【００４１】
まず、等価面積円直径［Ｄ］を、顕微鏡などで得られる像内で様々な形状で分散している個々の層状化合物の該顕微鏡像上での面積と等しい面積を有する円の直径であると定義する。その場合、ポリエステル樹脂組成物中に分散した層状化合物のうち、等価面積円直径［Ｄ］が３０００Å以下である層状化合物の数の比率は２０％以上であり、好ましくは３５％以上であり、さらに好ましくは５０％以上であり、特に好ましくは６５％以上である。等価面積円直径［Ｄ］が３０００Å以下である比率が２０％未満であるとポリエステル樹脂組成物の機械的特性の向上、反りの低減などの効果が充分でなくなる場合がある。また、本発明のポリエステル樹脂組成物中の層状化合物の等価面積円直径［Ｄ］の平均値は５０００Å以下であり、好ましくは４５００Å以下であり、さらに好ましくは４０００Å以下であり、特に好ましくは３５００Å以下である。等価面積円直径［Ｄ］の平均値が５０００Åより大きいとポリエステル樹脂組成物の機械的特性の改良効果が十分でなくなり、また表面外観が損なわれる場合がある。下限値は特にないが、おおよそ１００Å未満では効果はほとんど変わらなくなるので、１００Å未満にする必要はない。
【００４２】
等価面積円直径［Ｄ］の測定は、顕微鏡などを用いて撮影した像上で、１００個以上の層状化合物の層を含む任意の領域を選択し、画像処理装置などを用いて画像化して計算機処理することによって定量化できる。
【００４３】
平均アスペクト比を、樹脂中に分散した層状化合物の層長さ／層厚の比の数平均値であると定義すると、本発明のポリエステル樹脂組成物中の層状化合物の平均アスペクト比は１０〜３００であり、好ましくは１５〜３００であり。更に好ましくは２０〜３００である。層状化合物の平均アスペクト比が１０未満であると、本発明のポリエステル樹脂組成物の機械的特性などの改善効果が十分に得られない場合がある。また、３００より大きくても効果はそれ以上変わらないため、平均アスペクト比を３００より大きくする必要はない。
【００４４】
また、［Ｎ］値を、ポリエステル樹脂組成物の面積１００μｍ²における、層状化合物の単位重量比率当たりの分散粒子数であると定義すると、本発明のポリエステル樹脂組成物における層状化合物の［Ｎ］値は、３０以上であり、好ましくは４５以上であり、より好ましくは６０以上である。上限値は特にないが、［Ｎ］値が１０００程度を越えると、それ以上効果は変わらなくなるので、１０００より大きくする必要はない。［Ｎ］値が３０未満であるとポリエステル樹脂組成物の機械的特性や反りの改良効果が充分でなくなる場合がある。［Ｎ］値は、例えば、次のようにして求められ得る。すなわち、ポリエステル樹脂組成物を約５０μｍ〜１００μｍ厚の超薄切片に切り出し、該切片をＴＥＭ等で撮影した像上で、面積が１００μｍ²の任意の領域に存在する層状化合物の粒子数を、用いた層状化合物の重量比率で除すことによって求められ得る。あるいは、ＴＥＭ像上で、１００個以上の粒子が存在する任意の領域（面積は測定しておく）を選んで該領域に存在する粒子数を、用いた層状化合物の重量比率で除し、面積１００μｍ²に換算した値を［Ｎ］値としてもよい。従って、［Ｎ］値はポリエステル樹脂組成物のＴＥＭ写真等を用いることにより定量化できる。
【００４５】
また、平均層厚を、薄板状で分散した層状化合物の層厚みの数平均値であると定義すると、本発明のポリエステル樹脂組成物中の層状化合物の平均層厚の上限値は５００Å以下であり、好ましくは４５０Å以下であり、より好ましくは４００Å以下である。平均層厚が５００Åより大きいと、本発明のポリエステル樹脂組成物の機械的特性などの改良効果が十分に得られない場合がある。平均層厚の下限値は特に限定されないが、好ましくは５０Åより大きく、より好ましくは６０Å以上であり、更に好ましくは７０Å以上である。
【００４６】
また、最大層厚を、本発明のポリエステル樹脂組成物中に薄板状に分散した層状化合物の層厚みの最大値であると定義すると、層状化合物の最大層厚の上限値は、２０００Å以下であり、好ましくは１８００Å以下であり、より好ましくは１５００Å以下である。最大層厚が２０００Åより大きいと、本発明のポリエステル樹脂組成物の機械的特性、表面外観のバランスが損なわれる場合がある。層状化合物の最大層厚の下限値は特に限定されないが、好ましくは１００Åより大きく、より好ましくは１５０Å以上であり、更に好ましくは２００Å以上である。
【００４７】
層厚および層長さは、本発明のポリエステル樹脂組成物を加熱溶融した後に、熱プレス成形あるいは延伸成形して得られるフィルム、および溶融樹脂を射出成形して得られる薄肉の成形品等を、顕微鏡等を用いて撮影される像から求めることができる。
【００４８】
すなわち、いま仮に、Ｘ−Ｙ面上に上記の方法で調製したフィルムの、あるいは肉厚が約０．５〜２ｍｍ程度の薄い平板状の射出成形した試験片を置いたと仮定する。上記のフィルムあるいは試験片をＸ−Ｚ面あるいはＹ−Ｚ面と平行な面で約５０μｍ〜１００μｍ厚の超薄切片を切り出し、該切片を透過型電子顕微鏡などを用い、約４〜１０万倍以上の高倍率で観察して求められ得る。測定は、上記の方法で得られた透過型電子顕微鏡の象上に置いて、１００個以上の層状化合物を含む任意の領域を選択し、画像処理装置などで画像化し、計算機処理する事等により定量化できる。あるいは、定規などを用いて計測しても求めることもできる。
【００４９】
本発明で用いられるエポキシ基を有する化合物は特に限定されることはなく、ビスフェノールＡとエピクロルヒドリン等の反応により合成されるビスフェノールＡ型エポキシ樹脂、同様の反応により合成されるビスフェノールＦ型エポキシ樹脂、ノボラック樹脂とエピクロルヒドリン等の反応により合成されるノボラック型エポキシ樹脂、多価の脂肪族、脂環式、芳香族アルコールとエピクロルヒドリンとの反応により合成されるグリシジルエーテル化合物、不飽和基を複数個有する脂肪族もしくは脂環式化合物を酢酸と過酢酸とでエポキシ化して得られるエポキシ化合物、多価の脂肪族、脂環式、芳香族アミンとエピクロルヒドリンとの反応により合成されるグリシジルアミン化合物、含窒素ヘテロ環を複数個有する化合物とエピクロルヒドリンとの反応により合成して得られるエポキシ化合物などが挙げられる。
【００５０】
耐熱性の効果の点から、本発明で用いられるエポキシ化合物の分子中に含まれるエポキシ基は２個以上が好ましく、また、分子中にエステル結合を有しないほうが好ましい。
【００５１】
上記エポキシ化合物の具体例としては、例えばエピコート８２８、エピコート１００１、エピコート１５２（共に登録商標、油化シェルエポキシ株式会社）等のエポキシ樹脂、デナコールＥＭ−１２５、デナコールＥＸ−１１０１、デナコールＥＸ−１１０２、デナコールＥＸ−１１０３（共に登録商標、長瀬化成工業株式会社）等のエポキシエマルジョン、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、テトラメチレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、等のアルキレングリコールジグリシジルエーテル化合物、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ポリブタンジオールジグリシジルエーテル、ポリネオペンチルグリコールジグリシジルエーテル、ポリテトラメチレングリコールジグリシジルエーテル、等のポリアルキレングリコールジグリシジルエーテル化合物、レゾルシンジグリシジルエーテル、エリスリットポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ヒドロキノンジグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビタンポリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ビスフェノールＳジグリシジルエーテル、ジグリシジルアミン、テトラグリシジル４，４’−ジアミノジフェニルメタン、ジグリシジルアニリン、トリグリシジルトリス（２−ヒドロキシエチル）イソシアヌレート、等が挙げられる。これらは単独あるいは２種以上組み合わせて用いられ得る。
【００５２】
上記エポキシ化合物のエポキシ当量は、好ましくは７００以下、より好ましくは５００以下、更に好ましくは３００以下である。エポキシ当量が７００を超えると、耐湿熱性が劣る場合がある。
【００５３】
本発明のポリエステル樹脂組成物において、熱可塑性ポリエステル樹脂１００重量部に対して、上記エポキシ化合物の使用量の下限値は、０．０１重量部であり、好ましくは０．０５重量部であり、より好ましくは０．１重量部であり、更に好ましくは０．３重量部である。上限値は３０重量部であり、好ましくは２０重量部であり、より好ましくは１０重量部であり、更に好ましくは５重量部である。添加量の下限値が０．０１重量部より少ないと熱安定性の効果が得られ難くなり、上限値が３０重量部より多いと、機械的特性や成形品の表面が損なわれる場合がある。
【００５４】
本発明のポリエステル樹脂組成物の製造方法は特に制限されるものではなく、例えば、熱可塑性ポリエステル樹脂とポリエーテル化合物で処理した層状化合物およびエポキシ化合物とを、種々の一般的な混練機を用いて溶融混練する方法をあげることができる。混練機の例としては、一軸押出機、二軸押出機、ロール、バンバリーミキサー、ニーダーなどが挙げられ、特に、剪断効率の高い混練機が好ましい。混練する順番は特に限定されず、熱可塑性ポリエステル樹脂とエポキシ化合物および層状化合物は上記の混練機に一括投入して溶融混練してもよく、あるいは熱可塑性ポリエステル樹脂と層状化合物を混練した後にエポキシ化合物を添加混練してもよく、また、予め溶融状態にした熱可塑性ポリエステル樹脂に層状化合物およびエポキシ化合物を添加混練しても良い。
【００５５】
本発明のポリエステル樹脂組成物には、必要に応じて、ポリブタジエン、ブタジエン−スチレン共重合体、アクリルゴム、アイオノマー、エチレン−プロピレン共重合体、エチレン−プロピレン−ジエン共重合体、天然ゴム、塩素化ブチルゴム、α−オレフィンの単独重合体、２種以上のα−オレフィンの共重合体（ランダム、ブロック、グラフトなど、いずれの共重合体も含み、これらの混合物であっても良い）、またはオレフィン系エラストマーなどの耐衝撃性改良剤を添加することができる。これらは無水マレイン酸等の酸化合物で変性されていても良い。また、機械的特性、熱安定性などの特性を損なわない範囲で、他の任意の樹脂、例えば、不飽和ポリエステル樹脂、ポリエステルカーボネート樹脂、液晶ポリエステル樹脂、ポリオレフィン樹脂、ポリアミド樹脂、ゴム質重合体強化スチレン系樹脂、ポリフェニレンスルフィド樹脂、ポリフェニレンエーテル樹脂、ポリアセタール樹脂、ポリサルフォン樹脂、及びポリアリレート樹脂等を単独または２種以上組み合わせて使用し得る。
【００５６】
更に、本発明のポリエステル樹脂組成物には、目的に応じて、顔料や染料、紫外線吸収剤、光安定剤、滑剤、可塑剤、難燃剤および帯電防止剤等の添加剤を添加することができる。本発明のポリエステル樹脂組成物は、射出成形や熱プレス成形で成形しても良く、ブロー成形にも使用できる。
【００５７】
本発明のポリエステル樹脂組成物は各種の成形法により種々の形態、例えば各種成形品、シート、パイプ、ボトル等に成形することができる。また、本発明のポリエステル樹脂組成物は、高度な難燃性、成形流動性、外観、機械的特性および耐熱性に優れる為、例えば、自動車部品、家庭用電気製品部品、精密機械部品、家庭日用品、包装・容器資材、磁気記録テープ基材、その他一般工業用資材に好適に用いられる。
【００５８】
【実施例】
以下実施例により本発明を更に詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。
【００５９】
実施例、及び比較例で使用する主要原料を以下にまとめて示す。なお、特に断らない場合は、原料の精製は行っていない。
（原料）
・熱可塑性ポリエステル樹脂：ポリエチレンテレフタレート樹脂（鐘紡（株）のベルペットＥＦＧ７０、対数粘度（η_inh）＝０．７０（ｄｌ／ｇ）、以降ＰＥＴと称す）、ポリブチレンテレフタレート樹脂（ＫＯＬＯＮ社製のＫＰ２１０、以降ＰＢＴと称す）を用いた。
・層状化合物：モンモリロナイト（クニミネ工業（株）のクニピアＦ、以降クニピアＦと称す）および膨潤性雲母（コープケミカル（株）のソマシフＭＥ１００、以降ＭＥ１００と称す）を用いた。
・ポリエーテル化合物：主鎖にビスフェノールＡ単位を含有するポリエチレングリコール（東邦化学（株）のビスオール１８ＥＮ）を用いた。
・シラン系化合物：γ−（ポリオキシエチレン）プロピルトリメトキシシラン（日本ユニカー（株）のＡ−１２３０、以降Ａ１２３０と称す）を用いた。
・エポキシ化合物：ビスフェノールＡ型エポキシ樹脂（油化シェルエポキシ（株）のエピコート８２８）（エポキシ化合物Ｃ−１と称す）およびｏ−クレゾールノボラック型エポキシ樹脂（東都化成（株）のエポトートＹＤＣＮ７０４Ｐ）（エポキシ化合物Ｃ−２と称す）を用いた。
【００６０】
また、実施例および比較例における評価方法を以下にまとめて示す。
（分散状態の測定）
厚み５０〜１００μｍの超薄切片を用いた。透過型電子顕微鏡（日本電子ＪＥＭ−１２００ＥＸ）を用い、加速電圧８０ｋＶで倍率４万〜１００万倍で層状化合物の分散状態を観察撮影した。ＴＥＭ写真において、１００個以上の分散粒子が存在する任意の領域を選択し、層厚、層長、粒子数（［Ｎ］値）、等価面積円直径［Ｄ］を、目盛り付きの定規を用いた手計測またはインタークエスト社の画像解析装置ＰＩＡＳＩＩＩを用いて処理する事により測定した。
【００６１】
等価面積円直径［Ｄ］はインタークエスト社の画像解析装置ＰＩＡＳＩＩＩを用いて処理する事により測定した。［Ｎ］値の測定は以下のようにして行った。まず、ＴＥＭ像上で、選択した領域に存在する層状化合物の粒子数を求める。これとは別に、層状化合物に由来する樹脂組成物の灰分率を測定する。上記粒子数を灰分率で除し、面積１００μｍ²に換算した値を［Ｎ］値とした。平均層厚は個々の層状化合物の層厚の数平均値、最大層厚は個々の層状化合物の層厚の中で最大の値とした。分散粒子が大きく、ＴＥＭでの観察が不適当である場合は、光学顕微鏡（オリンパス光学（株）製の光学顕微鏡ＢＨ−２）を用いて上記と同様の方法で［Ｎ］値を求めた。ただし、必要に応じて、サンプルはＬＩＮＫＡＭ製のホットステージＴＨＭ６００を用いて２５０〜２７０℃で溶融させ、溶融状態のままで分散粒子の状態を測定した。板状に分散しない分散粒子のアスペクト比は、長径／短径の値とした。ここで、長径とは、顕微鏡像等において、対象となる粒子の外接する長方形のうち面積が最小となる長方形を仮定すれば、その長方形の長辺を意図する。また、短径とは、上記最小となる長方形の短辺を意図する。平均アスペクト比は個々の層状化合物の層長と層厚の比の数平均値とした。
（曲げ特性）
本発明のポリエステル樹脂組成物を乾燥（１４０℃、５時間）した。型締圧８０ｔの射出成形機を用い、シリンダー温度２５０〜２８０℃にて、厚み約６．４ｍｍ、幅約１２．７ｍｍ、長さ約１２７ｍｍの試験片を作製した。得られた試験片の曲げ特性を、ＡＳＴＭ Ｄ−７９０に従って測定した。
（溶融状態で滞留後の強度）
本発明のポリエステル樹脂組成物を乾燥（１４０℃、５時間）した。射出成形機のシリンダー内で２５０〜２７０℃で１５分間滞留した後に、上記と同条件で試験片を得、曲げ強度を測定した。
（溶融状態で滞留後の流動性）
本発明のポリエステル樹脂組成物を乾燥（１４０℃、５時間）した。島津製作所（株）のフローテスターを用い、ＰＥＴ系は温度２８０℃、ＰＰＴ系は温度２７０℃、ＰＢＴ系は温度２６０℃、それぞれ荷重１００ｋｇの条件でＢ法フロー値を測定し、滞留時間経時変化を調べた。この試験では、Ｂ法フロー値の変化が小さいほど好ましい。
（耐湿熱性）
１２１℃、１００％Ｒｈに設定したプレッシャークッカーで本発明のポリエステル樹脂組成物の試験片を３０時間高温高湿処理し、ＡＳＴＭ Ｄ−７９０に従って曲げ強度を測定した。
（反り）
本発明のポリエステル樹脂組成物を乾燥（１４０℃、５時間）した後、型締圧８０ｔの射出成形機を用い、金型温度１２０℃、シリンダー温度２５０〜２８０℃にて、寸法約１２０×１２０×１ｍｍの平板状試験片を作製した。平面上に上記の平板状試験片を置き、試験片の４隅の内の１カ所を押さえ、残り３隅の内、平面からの距離が最も大きい値を隙間ゲージやノギス等を用いて測定した。４隅それぞれを押さえ、得られた反り値の平均値を求めた。反り値は小さいほど優れている。
（表面光沢）
反りと同条件で成形した平板状試験片の表面光沢を測定した。ＥＲＩＣＨＳＥＮ社のミニグロスマスターを用い、反射角６０°で測定した。標準板５０％に対する相対値とした。表面光沢値は大きいほど優れている。
（灰分率）
無機物に由来する、ポリエステル樹脂組成物の灰分率は、ＪＩＳ Ｋ ７０５２に準じて測定した。
（製造例１）
反応機にＤＭＴ（ジメチルテレフタレート）、ＤＭＴ１００重量部に対し、７６重量部のプロピレングリコール、０．００３重量部のＡＯ６０（旭電化（株）のヒンダードフェノール系安定剤）および０．０００２５重量部のＴｉ（ＯＢｕ）₄を投入し、反応温度約１５０〜２００℃で撹拌してＤＭＴとプロピレングリコールをエステル交換させた。その後、０．０００２５重量部のＳｂ₂Ｏ₃を添加し、反応温度２７０〜２８０℃、減圧下（０．８〜５．０ｔｏｒｒ）で溶融重縮合を行い、ポリプロピレンテレフタレート（ＰＰＴ）樹脂を得た。
（製造例２）
イオン交換水と層状化合物を混合した。ついでポリエーテル化合物またはシラン系化合物を添加して１５〜６０分間混合を続ける事によって処理した。その後、粉体化して処理粘土（層状化合物Ａ−１〜Ａ−４）を得た。製造例で用いた原料の重量比は表１に示す。
【００６２】
【表１】

（実施例１〜７）
表２に示す重量比のＰＥＴ、製造例２で得た層状化合物（Ａ−１〜Ａ−４）、エポキシ化合物（Ｃ−１〜Ｃ−２）を二軸押出機（日本製鋼（株）製、ＴＥＸ４４）を用いて設定温度２３０〜２６０℃で溶融混練することによりポリエステル樹脂組成物を得、評価した。結果を表２に示す。
（比較例１〜３）
表２に示す重量比のＰＥＴ、ＭＥ１００、製造例２で得た層状化合物（Ａ−１）、エポキシ化合物（Ｃ−１）を実施例１と同様に溶融混練し、評価した。結果を表２に示す。
【００６３】
【表２】

表２より、ＭＥ１００をＰＥＴ樹脂と２軸押出して混練して得られる組成物は熱安定性は良いが、ＭＥ１００が薄片状に微分散していないために曲げ特性は改善されず、平板状の成形品は反りや表面光沢が測定できないほどに変形した。製造例２で得た層状化合物を用いた系では、初期物性は優れているが、溶融滞留後は粘度が低下するために加工性が不安定であり、滞留後および高温高湿処理後の強度低下がおこった。また、ＰＥＴ樹脂にエポキシ化合物を添加して得られた組成物は溶融状態で保持することにより粘度が増加し、成型加工性が悪化した。すなわち、ＰＥＴ樹脂にポリエーテル化合物で処理された層状化合物およびエポキシ基を有する化合物を配合することによって初めて諸物性のバランスに優れる樹脂組成物が得られる事が判る。
（実施例８〜１０）
表３に示す重量比のＰＢＴ、製造例２で得た層状化合物（Ａ−１、Ａ−３）、エポキシ化合物（Ｃ−１）を設定温度２２０〜２４０℃とした以外は実施例１と同様に溶融混練することによりポリエステル樹脂組成物を得、評価した。結果を表３に示す。
（比較例４〜６）
表３に示す重量比のＰＢＴ、ＭＥ１００、製造例２で得た層状化合物（Ａ−１）、エポキシ化合物（Ｃ−１）を実施例８と同様に溶融混練し、評価した。結果を表３に示す。
【００６４】
【表３】

表３より、ＭＥ１００をＰＢＴ樹脂と２軸押出して混練して得られる組成物（比較例４）は１５分滞留後の曲げ強度およびＢ法フロー値が滞留前と比較して変化が少ないので熱安定性は良いが、ＭＥ１００が薄片状に微分散していないために曲げ特性は改善されず、平板成形品の反りも改善されなかった。製造例２で得た層状化合物を用いた系では、初期物性は優れているが、溶融滞留後はＢ法フロー値が高まり、粘度が低下するために加工性が不安定であり、滞留後および高温高湿処理後の強度低下がおこった。また、エポキシ化合物を添加して得られた組成物は溶融状態で保持することによりＢ法フロー値が低下して粘度が増加し、成型加工性が悪化した。すなわち、ＰＢＴ樹脂にポリエーテル化合物で処理された層状化合物およびエポキシ基を有する化合物を配合することによって初めて諸物性のバランスに優れるポリエステル樹脂組成物が得られる事が判る。
（実施例１１）
表４に示す重量比の製造例１で得たＰＰＴ、製造例１で得た層状化合物（Ａ−１）、エポキシ化合物（Ｃ−１）を設定温度２２０〜２５０℃とした以外は実施例１と同様に溶融混練することによりポリエステル樹脂組成物を得、評価した。結果を表４に示す。
（比較例７〜９）
表４に示す重量比の製造例１で得たＰＰＴ、ＭＥ１００、製造例２で得た層状化合物（Ａ−１）およびエポキシ化合物（Ｃ−１）を実施例１１と同様に溶融混練し、評価した。結果を表４に示す。
【００６５】
【表４】

表４より、ＭＥ１００をＰＰＴ樹脂と２軸押出して混練して得られる組成物（比較例７）は１５分滞留後の曲げ強度およびＢ法フロー値が滞留前と比較して変化が少ないので熱安定性は良いが、ＭＥ１００が薄片状に微分散していないために曲げ特性は改善されず、平板成形品の反りも改善されなかった。製造例２で得た層状化合物を用いた系では、初期物性は優れているが、溶融滞留後はＢ法フロー値が高まり、粘度が低下するために加工性が不安定であり、滞留後および高温高湿処理後の強度低下がおこった。また、エポキシ化合物を添加して得られた組成物は溶融状態で保持することによりＢ法フロー値が低下して粘度が増加し、成型加工性が悪化した。すなわち、ＰＰＴ樹脂にポリエーテル化合物で処理された層状化合物およびエポキシ基を有する化合物を配合することによって初めて諸物性のバランスに優れるポリエステル樹脂組成物が得られる事が判る。
【００６６】
【発明の効果】
以上、詳述したように、熱可塑性ポリエステル樹脂、層状化合物およびエポキシ化合物を含む樹脂組成物中の層状化合物が下記（ａ）〜（ｃ）のうち少なくとも一方の条件を満たせば、熱安定性が良好となり、改良された機械的特性が溶融滞留後でも保持され、加えて反りも改良されかつ良好な表面外観を有する樹脂成形品を提供することができる。
（ａ）ポリエステル樹脂組成物中の層状化合物のうち、等価面積円直径［Ｄ］が３０００Å以下である層状化合物の比率が２０％以上であること
（ｂ）ポリエステル樹脂組成物中の層状化合物の等価面積円直径［Ｄ］の平均値が、５０００Å以下であること
（ｃ）［Ｎ］値が３０以上であり、ここで［Ｎ］値が、樹脂組成物の面積１００μｍ²中に存在する、層状化合物の単位比率当たりの粒子数であると定義されること。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyester resin composition containing a thermoplastic polyester resin, a layered compound, and a compound having an epoxy group.
[0002]
[Prior art]
Thermoplastic polyester resins such as polyethylene terephthalate are excellent in heat resistance, chemical resistance, weather resistance, mechanical properties, electrical properties, etc., so they are used in many industrial applications as injection molding materials, fibers, and films. Furthermore, higher mechanical properties and heat resistance are required. In general, attempts have been made to improve these requirements by blending various inorganic particles. However, the surface appearance of the product is impaired, and the orientation of the fibrous inorganic material during injection molding is anisotropic. There was a problem that caused sex.
[0003]
Such defects of inorganic particles are generally considered to be caused by poor dispersion of inorganic particles and excessively large dispersed particle size, and a technique for finely dispersing inorganic particles has been desired.
[0004]
Among inorganic particles, a layered compound, particularly a layered silicate, is a technique for making a layered silicate easy to cleave and finely disperse a polymer compound (intercalant polymer) such as polyvinylpyrrolidone. A technique (Japanese Patent Laid-Open No. 9-118518) that intercalates between acid salt layers to form an intercalation compound is disclosed. However, in the above invention, an intercalation compound is disclosed, but a technique for cleaving the intercalation compound to finely disperse it into a thermoplastic polyester resin is not disclosed, and a lamellar silicate in the thermoplastic polyester resin is not disclosed. It was difficult to finely disperse.
[0005]
In order to cleave and finely disperse the layered silicate layer in the thermoplastic polyester resin, the present researchers particularly treated the layered silicate with a polyether compound to form a clay intercalation compound. It has been found that it is effective, and a technique relating to a polyester resin composition containing a thermoplastic polyester resin and a clay intercalation compound has been disclosed (Japanese Patent Laid-Open Nos. 10-259016 and 10-310420). By this technique, mechanical characteristics and heat resistance can be enhanced without causing a decrease in surface appearance or warping. However, in the molten state, the thermoplastic polyester resin and the polyether compound react with each other to decompose the resin, so the thermal stability is not necessarily sufficient, and the viscosity of the resin decreases every time it passes through the molten state. In some cases, the workability becomes unstable and the strength also decreases.
[0006]
On the other hand, many techniques have been disclosed for increasing the molecular weight of a polyester resin that has been reduced in molecular weight by decomposition by using a polyfunctional compound having two or more epoxy groups or carbodiimide groups in the molecule (for example, JP No. 46-5389, JP-B 47-13860, etc.). It is generally known that the above technique is effective in maintaining the impact strength of a thermoplastic polyester resin, especially after being exposed to high temperature and high humidity conditions. However, the problem that the processability is unstable, such as a decrease in fluidity, has not been solved.
[0007]
[Problems to be solved by the invention]
The object of the present invention is to improve such a conventional problem, improve the mechanical properties without impairing the warp and surface appearance of the molded article of the thermoplastic polyester resin, improve the thermal stability in the molten state, and melt In addition to stabilizing the workability by stabilizing the viscosity, it is also intended to provide a polyester resin composition excellent in balance of physical properties by suppressing a decrease in strength during melt residence.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have completed the present invention.
[0009]
That is, the present invention is a polyester resin composition containing a thermoplastic polyester resin, a layered compound treated with a polyether compound, and a compound having an epoxy group, wherein the layered compounds are the following (a) to (c): The present invention relates to a polyester resin composition that satisfies at least one condition.
(A) Of the layered compounds in the polyester resin composition, the ratio of the layered compounds having an equivalent area circle diameter [D] of 3000 mm or less is 20% or more.
(B) The average value of the equivalent area circle diameter [D] of the layered compound in the polyester resin composition is 5000 mm or less.
(C) The [N] value is 30 or more, where the [N] value is an area of the resin composition of 100 μm.²Defined as the number of particles per unit ratio of layered compound present in
A preferred embodiment relates to the polyester resin composition as described above, wherein the layered compound has an average layer thickness of 500 mm or less.
[0010]
As a more preferred embodiment, the present invention relates to the polyester resin composition as described above, wherein the maximum thickness of the layered compound is 2000 mm or less.
[0011]
As a further preferred embodiment, the polyester resin composition according to any one of the above, wherein the average aspect ratio (ratio of layer length / layer thickness) of the layered compound in the resin composition is 10 to 300.
[0012]
As a further preferred embodiment, the polyester resin composition according to any one of the above, wherein the compound containing an epoxy group does not have an ester bond.
[0013]
As a more preferred embodiment, the layered compound is a layered silicate, which relates to the polyester resin composition according to any one of the above.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The thermoplastic polyester resin used in the present invention includes an acid component mainly composed of a dicarboxylic acid compound and / or an ester-forming derivative of dicarboxylic acid, and a diol compound and / or an ester-forming derivative of a diol compound as a main component. It is a conventionally well-known arbitrary thermoplastic polyester resin obtained by reaction with a diol component.
[0015]
With the said main component, the ratio which occupies in an acid component or a diol component intends that it is 80% or more, Furthermore, 90% or more, and an upper limit is 100%.
[0016]
Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, and 4,4 ′. -Diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-diphenylisopropylidenedicarboxylic acid, etc., and their substitutes (for example, alkyl group substitutes such as methylisophthalic acid) and derivatives (Alkyl ester compounds such as dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate) can also be used. Oxy acids such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid and ester-forming derivatives thereof can also be used. Two or more of these monomers may be mixed and used. If the amount is small enough not to impair the properties of the resulting polyester resin composition, these aromatic dicarboxylic acids are mixed with one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid, sebacic acid, etc. And can be used.
[0017]
Among the above acid components, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and ester-forming derivatives thereof from the viewpoints of crystallinity, strength, and elastic modulus of the obtained polyester resin Is preferred.
[0018]
Examples of the glycol compound include aliphatic glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and neopentyl glycol, and alicyclic glycols such as 1,4-cyclohexanedimethanol. These substitutions and derivatives can also be used. Cyclic esters such as ε-caprolactone can also be used. Two or more of these may be mixed and used. Furthermore, if the amount is small enough not to significantly reduce the elastic modulus of the polyester resin, a long-chain diol compound (for example, polyethylene glycol, polytetramethylene glycol), an alkylene oxide addition polymer of bisphenols (for example, A combination of an ethylene oxide addition polymer of bisphenol A and the like may be used.
[0019]
Among the diol components, ethylene glycol, butylene glycol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane are used from the viewpoints of handleability and the strength and elastic modulus of the resulting polyester resin. Is preferred.
[0020]
Specific examples of the thermoplastic polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, neopentyl terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene naphthalate. Examples thereof include phthalate, polyhexamethylene naphthalate, and the like, or a copolymer polyester thereof. You may use them individually or in combination of 2 or more types.
[0021]
The molecular weight of the thermoplastic polyester resin is selected in consideration of the molding fluidity in the molding process and various physical properties of the final product, and it is not preferable whether it is too low or too high, and it is necessary to set a suitable molecular weight. That is, the molecular weight of the thermoplastic polyester resin has a logarithmic viscosity of 0.3 to 2.0 (dl / g) measured at 25 ° C. using a phenol / tetrachloroethane (5/5 weight ratio) mixed solvent, Preferably it is 0.35-1.9 (dl / g), More preferably, it is 0.4-1.8 (dl / g). When the logarithmic viscosity is less than 0.3 (dl / g), the mechanical properties of the resulting molded product of the polyester resin composition are low, and when it is greater than 2.0 (dl / g), the fluidity at the time of molding. There is a tendency for problems to occur in processability.
[0022]
The layered compound used in the present invention is a silicate, a phosphate such as zirconium phosphate, a titanate such as potassium titanate, a tungstate such as sodium tungstate, a uranate such as sodium uranate, One or more selected from the group consisting of vanadate such as potassium vanadate, molybdate such as magnesium molybdate, niobate such as potassium niobate, and graphite. A layered silicate is preferably used from the viewpoint of easy availability and handling.
[0023]
The layered silicate is formed mainly from a tetrahedral sheet of silicon oxide and an octahedral sheet of metal hydroxide, and examples thereof include smectite clay and swellable mica.
[0024]
The smectite clay is represented by the following general formula (1)
X1_0.2~_0.6Y1₂~_ThreeZ1_FourO_Ten(OH)₂・ NH₂O (1)
(However, X1 is at least one selected from the group consisting of K, Na, 1 / 2Ca, and 1 / 2Mg, and Y1 is a group consisting of Mg, Fe, Mn, Ni, Zn, Li, Al, and Cr. One or more selected from Z and Z1 is one or more selected from the group consisting of Si and Al.₂O represents a water molecule bonded to an interlayer ion, and n represents a natural or synthesized substance represented by (varies depending on the interlayer ion and relative humidity). Specific examples of the smectite group clay include, for example, montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, soconite, stevensite, bentonite, and the like, or substitution products, derivatives, or mixtures thereof. . The bottom surface interval in the initial aggregated state of the smectite group clay is about 10 to 17 mm, and the average particle size of the smectite group clay in the aggregated state is about 1,000 to 1,000,000 mm.
[0025]
Further, the swellable mica is represented by the following general formula (2)
X2_0.5~_1.0Y2₂~_Three(Z2_FourO_Ten) (F, OH)₂                 (2)
(However, X2 is at least one selected from the group consisting of Li, Na, K, Rb, Ca, Ba, and Sr, and Y2 is selected from the group consisting of Mg, Fe, Ni, Mn, Al, and Li) Z2 is one or more selected from the group consisting of Si, Ge, Al, Fe, and B.) or natural or synthesized. These are water, a polar solvent that is compatible with water at an arbitrary ratio, and a material that swells in a mixed solvent of water and the polar solvent. For example, lithium-type teniolite, sodium-type teniolite, lithium-type four Examples thereof include silicon mica and sodium-type tetrasilicon mica, or substituted products, derivatives, or mixtures thereof. The distance between the bottom surfaces in the initial aggregated state of the swellable mica is about 10 to 17 mm, and the average particle size of the swellable mica in the aggregated state is about 1,000 to 1,000,000 mm.
[0026]
Some of the above swellable mica have a structure similar to vermiculites, and such vermiculites and the like can also be used. The vermiculite-equivalent products are classified into 3 octahedron type and 2 octahedron type, and the following general formula (3)
(Mg, Fe, Al)₂~_Three(Si_4-xAlx) O_Ten(OH)₂・ (M⁺, M²⁺ _1/2)_x・ NH₂O (3)
(Wherein M is an exchangeable cation of an alkali or alkaline earth metal such as Na and Mg, x = 0.6 to 0.9, and n = 3.5 to 5). . The bottom surface interval in the initial aggregation state of the vermiculite equivalent product is approximately 10 to 17 mm, and the average particle size in the aggregation state is approximately 1,000 to 5,000,000 mm.
[0027]
The crystal structure of the layered silicate is preferably a highly pure layer that is regularly stacked in the c-axis direction, but so-called mixed layer minerals in which the crystal period is disturbed and a plurality of types of crystal structures are mixed can also be used.
[0028]
A layered silicate may be used independently and may be used in combination of 2 or more type. Among these, montmorillonite, bentonite, hectorite, and swellable mica having sodium ions between layers are preferable from the viewpoint of the dispersibility in the obtained polyester resin composition and the effect of improving the physical properties of the polyester resin composition.
[0029]
The above polyether compound is intended to be a compound whose main chain is polyoxyalkylene such as polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer, and has a repeating unit number of about 2 to 100 Intended. The polyether compound may have an arbitrary substituent in the side chain and / or main chain as long as it does not adversely affect the thermoplastic polyester resin or the layered compound. Examples of the substituent include a hydrocarbon group, a group bonded by an ester bond, an epoxy group, an amino group, a carboxyl group, a group having a carbonyl group at the terminal, an amide group, a mercapto group, and a sulfonyl bond. Groups containing sulfinyl bonds, nitro groups, nitroso groups, nitrile groups, alkoxysilyl groups, silanol groups, Si-containing atom functional groups that can form Si-O- bonds, halogen atoms, hydroxyl groups, etc. Can be mentioned. One of these may be substituted, or two or more may be substituted.
[0030]
The above-mentioned hydrocarbon group is a linear or branched (that is, having a side chain) saturated or unsaturated monovalent or polyvalent aliphatic hydrocarbon group, aromatic hydrocarbon group, or alicyclic hydrocarbon group. And examples thereof include an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, a naphthyl group, and a cycloalkyl group. In the present specification, the term “alkyl group” is intended to include a polyvalent hydrocarbon group such as an “alkylene group” unless otherwise specified. Similarly, an alkenyl group, an alkynyl group, a phenyl group, a naphthyl group, and a cycloalkyl group include an alkenylene group, an alkynylene group, a phenylene group, a naphthylene group, and a cycloalkylene group, respectively.
[0031]
The composition ratio of the substituents in the polyether compound is not particularly limited, but it is desirable that the polyether compound is soluble in water or a polar solvent containing water. Specifically, for example, the solubility in 100 g of water at room temperature is 1 g or more, preferably 2 g or more, more preferably 5 g or more, still more preferably 10 g or more, and particularly preferably 20 g or more. . Examples of the polar solvent include alcohols such as methanol, ethanol, and isopropanol, glycols such as ethylene glycol, propylene glycol, and 1,4-butanediol, ketones such as acetone and methyl ethyl ketone, diethyl ether, and tetrahydrofuran. Examples of ethers, amide compounds such as N, N-dimethylformamide and N, N-dimethylacetamide, and other solvents include pyridine, dimethyl sulfoxide and N-methylpyrrolidone. Carbonic acid diesters such as dimethyl carbonate and diethyl carbonate can also be used. These polar solvents may be used alone or in combination of two or more.
[0032]
Specific examples of the polyether compound used in the present invention include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol, polyethylene glycol-polytetramethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol. Monoethyl ether, polyethylene glycol diethyl ether, polyethylene glycol monoallyl ether, polyethylene glycol diallyl ether, polyethylene glycol monophenyl ether, polyethylene glycol diphenyl ether, polyethylene glycol octylphenyl ether, polyethylene glycol methyl ethyl ether, poly Tylene glycol methyl allyl ether, polyethylene glycol glyceryl ether, polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, polypropylene glycol monomethacrylate, polypropylene glycol monoacrylate, polyethylene glycol-polypropylene glycol monomethacrylate, polyethylene glycol-polypropylene glycol monoacrylate, polyethylene glycol- Polytetramethylene glycol monomethacrylate, polyethylene glycol-polytetramethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, methoxypolyethylene glycol monoacrylate, octoxypolyethylene glycol-polypropylene Lenglycol monomethacrylate, octoxypolyethyleneglycol-polypropyleneglycolmonoacrylate, lauroxypolyethyleneglycolmonomethacrylate, lauroxypolyethyleneglycolmonoacrylate, stearoxypolyethyleneglycolmonomethacrylate, stearoxypolyethyleneglycolmonoacrylate, allyloxypolyethyleneglycolmonomethacrylate, Allyloxy polyethylene glycol monoacrylate, nonylphenoxy polyethylene glycol monomethacrylate, nonylphenoxy polyethylene glycol monoacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol-polytetramethylene glycol di Methacrylate, polyethylene glycol-polytetramethylene glycol diacrylate, bis (polyethylene glycol) butylamine, bis (polyethylene glycol) octylamine, polyethylene glycol bisphenol A ether, polyethylene glycol-polypropylene glycol bisphenol A ether, ethylene oxide modified bisphenol A dimethacrylate, Ethylene oxide modified bisphenol A diacrylate, ethylene oxide-propylene oxide modified bisphenol A dimethacrylate, polyethylene glycol diglycidyl ether, polyethylene glycol ureidopropyl ether, polyethylene glycol mercaptopropyl ether, polyethylene glycol phenylsulfonyl Ropirueteru, polyethylene glycol phenylsulfinyl propyl ether, polyethylene glycol nitro propyl ether, polyethylene glycol nitroso propyl ether, polyethylene glycol cyanoethyl ethers, polyethylene glycol cyanoethyl ether. These polyether compounds may be used alone or in combination of two or more. Among the polyether compounds of the present invention, those having a cyclic hydrocarbon group such as an aromatic hydrocarbon group or an alicyclic hydrocarbon group are preferred, and among them, the following general formula (4)
[0033]
[Chemical 1]

(In the formula, -A- represents -O-, -S-, -SO-, -SO.₂-, -CO-, an alkylene group having 1 to 20 carbon atoms, or an alkylidene group having 6 to 20 carbon atoms, and R¹, R², R^Three, R^Four, R^Five, R⁶, R⁷And R⁸Are all hydrogen atoms, halogen atoms, or monovalent hydrocarbon groups having 1 to 5 carbon atoms;⁹, R^TenAre all divalent hydrocarbon groups having 1 to 5 carbon atoms, R¹¹, R¹²Are hydrogen atoms and monovalent hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different. m and n represent the number of repeating units of oxyalkylene units, and 2 ≦ m + n ≦ 50. )
Is preferable from the viewpoint of the dispersibility and thermal stability of the layered compound.
[0034]
The amount of the polyether compound used can be adjusted so that the affinity between the layered compound and the thermoplastic polyester resin and the dispersibility of the layered compound in the polyester resin composition are sufficiently enhanced. If necessary, a plurality of types of polyether compounds having different functional groups can be used in combination. Therefore, although the amount of the polyether compound used is not generally limited by a numerical value, the lower limit of the amount of the polyether compound added relative to 100 parts by weight of the layered compound is 0.1 part by weight, preferably 0.8. 2 parts by weight, more preferably 0.3 parts by weight, still more preferably 0.4 parts by weight, and particularly preferably 0.5 parts by weight. The upper limit of the amount of the layered compound to 100 parts by weight of the layered compound is 200 parts by weight, preferably 180 parts by weight, more preferably 160 parts by weight, still more preferably 140 parts by weight, particularly preferably. Is 120 parts by weight. If the lower limit of the amount of the polyether compound is less than 0.1 parts by weight, the effect of finely dispersing the layered compound tends to be insufficient. Further, since the effect does not change when the amount of the polyether compound is 200 parts by weight or more, it is not necessary to use more than 200 parts by weight.
[0035]
The method of mixing the layered compound and the polyether compound is not particularly limited, and a method of directly mixing the layered compound and the polyether compound or a method of mixing the layered compound and the polyether compound in water or a polar solvent containing water. Can be mentioned. The latter is desirable from the viewpoint of mixing efficiency. In the present invention, the method for treating a layered compound with a polyether compound is not particularly limited, and for example, the method shown below can be used.
[0036]
First, the layered compound and the dispersion medium are mixed with stirring. The dispersion medium is intended to be water or a polar solvent containing water. Specifically, since it has already been described above, it is omitted here.
[0037]
The method for stirring the layered compound and the dispersion medium is not particularly limited, and for example, it is performed using a conventionally known wet stirrer. Examples of the wet stirrer include a high speed stirrer in which a stirring blade rotates at a high speed, a wet mill that wet-grinds a sample in a gap between a rotor and a stator that is subjected to a high shear rate, and a mechanical that uses a hard medium. Examples include wet pulverizers, wet collision pulverizers that cause a sample to collide at high speed with a jet nozzle, and wet ultrasonic pulverizers that use ultrasonic waves. In order to mix more efficiently, the rotation speed of stirring is 1000 rpm or more, preferably 1500 rpm or more, more preferably 2000 rpm or more, or 500 (1 / s) or more, preferably 1000 (1 / s) or more, More preferably, a shear rate of 1500 (1 / s) or more is applied. The upper limit of the rotational speed is about 25000 rpm, and the upper limit of the shear rate is about 500,000 (1 / s). Stirring at a value larger than the upper limit is not necessary because stirring tends to be performed at a value larger than the upper limit or no further change occurs even when shearing is applied. Moreover, the time which mixing requires is 1 to 10 minutes or more. Next, after adding the polyether compound, stirring is continued under the same conditions, and the mixture is thoroughly mixed. The temperature at the time of mixing is sufficient at room temperature, but may be heated as necessary. The maximum temperature during heating can be arbitrarily set as long as it is lower than the decomposition temperature of the polyether compound used and lower than the boiling point of the dispersion medium. Then, it dries and pulverizes as needed.
[0038]
In the polyester resin composition of the present invention, the lower limit of the compounding amount of the layered compound treated with the polyether compound with respect to 100 parts by weight of the thermoplastic polyester resin is typically 0.1 parts by weight, preferably 0. 3 parts by weight, more preferably 0.5 parts by weight, still more preferably 1.0 parts by weight, and particularly preferably 1.5 parts by weight. The upper limit of the amount is typically 150 parts by weight, preferably 100 parts by weight, more preferably 70 parts by weight, still more preferably 50 parts by weight, and particularly preferably 30 parts by weight. To be prepared. If the lower limit of the amount of the layered compound is less than 0.1 parts by weight, improvement effects such as improvement of mechanical properties and reduction of warpage may be insufficient, and if the upper limit exceeds 150 parts by weight, molding is performed. The surface appearance of the body tends to be impaired.
[0039]
Further, the lower limit of the ash content of the polyester resin composition derived from the layered compound is typically 0.1% by weight, preferably 0.3% by weight, more preferably 0.5% by weight. More preferably 1.0% by weight, particularly preferably 1.5% by weight, and the upper limit of the ash content is 60% by weight, preferably 50% by weight, more It is preferably 40% by weight, more preferably 30% by weight. If the lower limit of the ash content is less than 0.1% by weight, improvement effects such as improvement of mechanical properties and reduction of warpage may be insufficient. If the upper limit exceeds 60% by weight, the surface of the molded body Appearance tends to be impaired.
[0040]
The structure of the layered compound dispersed in the polyester resin composition of the present invention is completely different from the μm-sized aggregated structure in which a large number of layers are stacked as the layered compound before use has. That is, by treating with a polyether compound, the layers are cleaved and subdivided independently of each other. As a result, the layered compound is dispersed in the polyester resin composition in the form of a very fine and independent thin plate, and the number thereof is significantly increased compared to the layered compound before use. The dispersion state of such a lamellar layered compound is expressed by the equivalent area circle diameter [D], aspect ratio (layer length / layer thickness ratio), number of dispersed particles, maximum layer thickness and average layer thickness described below. obtain.
[0041]
First, the equivalent area circle diameter [D] is the diameter of a circle having an area equal to the area on the microscopic image of each layered compound dispersed in various shapes in an image obtained by a microscope or the like. Define. In that case, among the layered compounds dispersed in the polyester resin composition, the ratio of the number of layered compounds having an equivalent area circle diameter [D] of 3000 mm or less is 20% or more, preferably 35% or more, Preferably it is 50% or more, Most preferably, it is 65% or more. When the ratio of the equivalent area circle diameter [D] of 3000 mm or less is less than 20%, the polyester resin composition may have insufficient effects such as improvement of mechanical properties and reduction of warpage. The average value of the equivalent area circle diameter [D] of the layered compound in the polyester resin composition of the present invention is 5000 mm or less, preferably 4500 mm or less, more preferably 4000 mm or less, and particularly preferably 3500 mm or less. It is. When the average value of the equivalent area circle diameter [D] is larger than 5000 mm, the effect of improving the mechanical properties of the polyester resin composition is not sufficient, and the surface appearance may be impaired. There is no particular lower limit, but the effect is hardly changed below about 100 mm, so it is not necessary to set it below 100 mm.
[0042]
The equivalent area circle diameter [D] is measured by selecting an arbitrary region including 100 or more layers of a layered compound on an image photographed using a microscope and imaging the image using an image processing apparatus or the like. It can be quantified by processing.
[0043]
When the average aspect ratio is defined as the number average value of the ratio of the layer length / layer thickness of the layered compound dispersed in the resin, the average aspect ratio of the layered compound in the polyester resin composition of the present invention is 10 to 300. Preferably, it is 15-300. More preferably, it is 20-300. If the average aspect ratio of the layered compound is less than 10, there may be a case where the effect of improving the mechanical properties of the polyester resin composition of the present invention cannot be sufficiently obtained. Moreover, since the effect does not change any more than 300, it is not necessary to make the average aspect ratio larger than 300.
[0044]
In addition, the [N] value is set to an area of 100 μm of the polyester resin composition²In the polyester resin composition of the present invention, the [N] value of the layered compound is 30 or more, preferably 45 or more, and more preferably defined as the number of dispersed particles per unit weight ratio of the layered compound. Is 60 or more. There is no particular upper limit, but if the [N] value exceeds about 1000, the effect does not change any more, so it is not necessary to make it larger than 1000. If the [N] value is less than 30, the effect of improving the mechanical properties and warpage of the polyester resin composition may not be sufficient. The [N] value can be obtained, for example, as follows. That is, the polyester resin composition was cut into ultra-thin sections having a thickness of about 50 μm to 100 μm, and the area was 100 μm on an image taken with a TEM or the like.²It can be obtained by dividing the number of particles of the layered compound present in any region of the above by the weight ratio of the layered compound used. Alternatively, on the TEM image, an arbitrary region (the area is measured) in which 100 or more particles are present is selected, and the number of particles present in the region is divided by the weight ratio of the layered compound used. 100 μm²The value converted into may be the [N] value. Therefore, the [N] value can be quantified by using a TEM photograph or the like of the polyester resin composition.
[0045]
Moreover, when the average layer thickness is defined as the number average value of the layer thicknesses of the lamellar compound dispersed in a thin plate shape, the upper limit value of the average layer thickness of the layer compound in the polyester resin composition of the present invention is 500 mm or less. , Preferably 450 mm or less, more preferably 400 mm or less. If the average layer thickness is greater than 500 mm, there may be a case where a sufficient improvement effect such as mechanical properties of the polyester resin composition of the present invention cannot be obtained. The lower limit value of the average layer thickness is not particularly limited, but is preferably larger than 50 mm, more preferably 60 mm or more, and further preferably 70 mm or more.
[0046]
When the maximum layer thickness is defined as the maximum value of the layer thickness of the layered compound dispersed in a thin plate shape in the polyester resin composition of the present invention, the upper limit value of the maximum layer thickness of the layered compound is 2000 mm or less. , Preferably it is 1800 or less, More preferably, it is 1500 or less. When the maximum layer thickness is larger than 2000 mm, the balance of mechanical properties and surface appearance of the polyester resin composition of the present invention may be impaired. The lower limit value of the maximum layer thickness of the layered compound is not particularly limited, but is preferably more than 100 mm, more preferably 150 mm or more, and further preferably 200 mm or more.
[0047]
The layer thickness and the layer length are obtained by heating and melting the polyester resin composition of the present invention, followed by hot press molding or stretch molding, and a thin molded product obtained by injection molding of the molten resin. It can be obtained from an image photographed using a microscope or the like.
[0048]
That is, it is assumed that a thin plate-shaped injection-molded test piece having a thickness of about 0.5 to 2 mm is placed on the XY plane. The film or test piece is cut into an ultrathin section having a thickness of about 50 μm to 100 μm in a plane parallel to the XZ plane or the YZ plane, and the section is cut about 4 to 100,000 times using a transmission electron microscope or the like. It can be obtained by observing at the above high magnification. The measurement is carried out by placing on an elephant of a transmission electron microscope obtained by the above method, selecting an arbitrary region containing 100 or more layered compounds, forming an image with an image processing apparatus, and performing computer processing. It can be quantified. Alternatively, it can be obtained by measurement using a ruler or the like.
[0049]
The compound having an epoxy group used in the present invention is not particularly limited. A bisphenol A type epoxy resin synthesized by a reaction of bisphenol A and epichlorohydrin, a bisphenol F type epoxy resin synthesized by the same reaction, or a novolak Novolac type epoxy resin synthesized by reaction of resin and epichlorohydrin, etc., polyvalent aliphatic, alicyclic, glycidyl ether compound synthesized by reaction of aromatic alcohol and epichlorohydrin, aliphatic having plural unsaturated groups Alternatively, an epoxy compound obtained by epoxidizing an alicyclic compound with acetic acid and peracetic acid, a polyvalent aliphatic, alicyclic, glycidylamine compound synthesized by a reaction of an aromatic amine and epichlorohydrin, a nitrogen-containing heterocycle A compound having a plurality of And epoxy compounds obtained by synthesizing by reaction with phosphorus and the like.
[0050]
From the viewpoint of the effect of heat resistance, two or more epoxy groups are preferably included in the molecule of the epoxy compound used in the present invention, and it is preferable that the molecule does not have an ester bond.
[0051]
Specific examples of the epoxy compound include, for example, epoxy resins such as Epicoat 828, Epicoat 1001, Epicoat 152 (both are registered trademarks, Yuka Shell Epoxy Co., Ltd.), Denacol EM-125, Denacol EX-1101, Denacol EX-1102, Epoxy emulsions such as Denacol EX-1103 (both are registered trademarks, Nagase Kasei Kogyo Co., Ltd.), ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6- Hexanediol diglycidyl ether, alkylene glycol diglycidyl ether compounds such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycol Polyalkylene glycol diglycidyl ether compounds such as dil ether, polybutanediol diglycidyl ether, polyneopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcin diglycidyl ether, erythritol polyglycidyl ether, trimethylolpropane Polyglycidyl ether, pentaerythritol polyglycidyl ether, hydroquinone diglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, sorbitol polyglycidyl ether, bisphenol S diglycidyl ether, diglycidyl amine, tetraglycidyl 4 , 4'-Diaminodiphenylmethane, Digly Jiruanirin, triglycidyl tris (2-hydroxyethyl) isocyanurate, and the like. These may be used alone or in combination of two or more.
[0052]
The epoxy equivalent of the epoxy compound is preferably 700 or less, more preferably 500 or less, and still more preferably 300 or less. When the epoxy equivalent exceeds 700, the heat and humidity resistance may be inferior.
[0053]
In the polyester resin composition of the present invention, the lower limit of the amount of the epoxy compound used relative to 100 parts by weight of the thermoplastic polyester resin is 0.01 parts by weight, preferably 0.05 parts by weight. Preferably it is 0.1 weight part, More preferably, it is 0.3 weight part. The upper limit is 30 parts by weight, preferably 20 parts by weight, more preferably 10 parts by weight, and still more preferably 5 parts by weight. If the lower limit of the addition amount is less than 0.01 parts by weight, it is difficult to obtain the effect of thermal stability, and if the upper limit is more than 30 parts by weight, the mechanical properties and the surface of the molded product may be impaired.
[0054]
The production method of the polyester resin composition of the present invention is not particularly limited. For example, a layered compound and an epoxy compound treated with a thermoplastic polyester resin and a polyether compound are used with various general kneaders. A method of melt kneading can be mentioned. Examples of the kneader include a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, a kneader, and the like, and a kneader with high shear efficiency is particularly preferable. The order of kneading is not particularly limited, and the thermoplastic polyester resin, the epoxy compound, and the layered compound may be put into the kneading machine and melt-kneaded or the epoxy compound after kneading the thermoplastic polyester resin and the layered compound. The layered compound and the epoxy compound may be added and kneaded to the thermoplastic polyester resin previously melted.
[0055]
The polyester resin composition of the present invention includes polybutadiene, butadiene-styrene copolymer, acrylic rubber, ionomer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, natural rubber, chlorination as necessary. Butyl rubber, α-olefin homopolymer, copolymer of two or more α-olefins (including any copolymer such as random, block, graft, etc., or a mixture thereof), or olefinic An impact modifier such as an elastomer can be added. These may be modified with an acid compound such as maleic anhydride. In addition, other optional resins such as unsaturated polyester resin, polyester carbonate resin, liquid crystal polyester resin, polyolefin resin, polyamide resin, rubbery polymer reinforced, as long as the properties such as mechanical properties and thermal stability are not impaired. Styrenic resins, polyphenylene sulfide resins, polyphenylene ether resins, polyacetal resins, polysulfone resins, polyarylate resins, and the like can be used alone or in combination of two or more.
[0056]
Furthermore, additives such as pigments and dyes, UV absorbers, light stabilizers, lubricants, plasticizers, flame retardants and antistatic agents can be added to the polyester resin composition of the present invention. . The polyester resin composition of the present invention may be molded by injection molding or hot press molding, and can also be used for blow molding.
[0057]
The polyester resin composition of the present invention can be molded into various forms, for example, various molded products, sheets, pipes, bottles, and the like by various molding methods. Further, since the polyester resin composition of the present invention is excellent in high flame retardancy, molding fluidity, appearance, mechanical properties and heat resistance, for example, automobile parts, household electrical appliance parts, precision machine parts, household daily goods. It is suitably used for packaging / container materials, magnetic recording tape base materials, and other general industrial materials.
[0058]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
[0059]
The main raw materials used in Examples and Comparative Examples are summarized below. Unless otherwise noted, the raw materials are not purified.
(material)
-Thermoplastic polyester resin: Polyethylene terephthalate resin (bellpet EFG70 from Kanebo Co., Ltd., logarithmic viscosity (η_inh) = 0.70 (dl / g), hereinafter referred to as PET), and polybutylene terephthalate resin (KP210 manufactured by KOLON, hereinafter referred to as PBT) was used.
Layered compound: Montmorillonite (Kunimine F Co., Ltd. Kunipia F, hereinafter referred to as Kunipia F) and swelling mica (Coop Chemical Co., Ltd. Somasif ME100, hereinafter referred to as ME100) were used.
Polyether compound: Polyethylene glycol containing bisphenol A unit in the main chain (Bisol 18EN from Toho Chemical Co., Ltd.) was used.
Silane-based compound: γ- (polyoxyethylene) propyltrimethoxysilane (A-1230 of Nippon Unicar Co., Ltd., hereinafter referred to as A1230) was used.
Epoxy compounds: bisphenol A type epoxy resin (Epicoat 828 of Yuka Shell Epoxy Co., Ltd.) (referred to as epoxy compound C-1) and o-cresol novolac type epoxy resin (Epototo YDCN704P of Toto Kasei Co., Ltd.) (epoxy) Compound C-2) was used.
[0060]
Moreover, the evaluation method in an Example and a comparative example is shown collectively below.
(Distributed state measurement)
Ultrathin sections with a thickness of 50-100 μm were used. Using a transmission electron microscope (JEOL JEM-1200EX), the dispersion state of the layered compound was observed and photographed at an acceleration voltage of 80 kV and a magnification of 40,000 to 1,000,000 times. In a TEM photograph, select an arbitrary region where 100 or more dispersed particles exist, and use a ruler with a scale for layer thickness, layer length, number of particles ([N] value), equivalent area circle diameter [D]. The measurement was performed by hand measurement or by using an image analysis apparatus PIASIII manufactured by Interquest.
[0061]
The equivalent area circle diameter [D] was measured by processing using an image analysis apparatus PIASIII manufactured by Interquest. The [N] value was measured as follows. First, the number of particles of the layered compound present in the selected region is determined on the TEM image. Separately from this, the ash content of the resin composition derived from the layered compound is measured. Dividing the number of particles by the ash content, the area is 100 μm²The value converted to was defined as [N] value. The average layer thickness was the number average value of the layer thicknesses of the individual layer compounds, and the maximum layer thickness was the maximum value among the layer thicknesses of the individual layer compounds. When the dispersed particles are large and observation with a TEM is inappropriate, the [N] value was obtained by the same method as described above using an optical microscope (an optical microscope BH-2 manufactured by Olympus Optical Co., Ltd.). However, if necessary, the sample was melted at 250 to 270 ° C. using a hot stage THM600 manufactured by LINKAM, and the state of dispersed particles was measured in the molten state. The aspect ratio of the dispersed particles that are not dispersed in a plate shape is a value of major axis / minor axis. Here, the major axis means a long side of a rectangle assuming a rectangle having a minimum area among rectangles circumscribing target particles in a microscopic image or the like. Further, the short diameter means the short side of the rectangle that is the minimum. The average aspect ratio was the number average value of the ratio between the layer length and the layer thickness of each layered compound.
(Bending characteristics)
The polyester resin composition of the present invention was dried (140 ° C., 5 hours). Using an injection molding machine with a clamping pressure of 80 t, a test piece having a thickness of about 6.4 mm, a width of about 12.7 mm, and a length of about 127 mm was produced at a cylinder temperature of 250 to 280 ° C. The bending properties of the resulting specimen were measured according to ASTM D-790.
(Strength after residence in molten state)
The polyester resin composition of the present invention was dried (140 ° C., 5 hours). After staying at 250-270 ° C. for 15 minutes in the cylinder of the injection molding machine, a test piece was obtained under the same conditions as described above, and the bending strength was measured.
(Fluidity after residence in molten state)
The polyester resin composition of the present invention was dried (140 ° C., 5 hours). Using a flow tester manufactured by Shimadzu Corporation, measure the B method flow value under the conditions of a temperature of 280 ° C for the PET system, a temperature of 270 ° C for the PPT system, a temperature of 260 ° C for the PBT system, and a load of 100 kg. I investigated. In this test, the smaller the change in the B method flow value, the better.
(Moisture and heat resistance)
A test piece of the polyester resin composition of the present invention was treated at a high temperature and high humidity for 30 hours with a pressure cooker set at 121 ° C. and 100% Rh, and the bending strength was measured according to ASTM D-790.
(warp)
After drying the polyester resin composition of the present invention (140 ° C., 5 hours), using an injection molding machine with a clamping pressure of 80 t, at a mold temperature of 120 ° C. and a cylinder temperature of 250 to 280 ° C., dimensions of about 120 × 120 A 1 mm flat plate test piece was prepared. Place the above-mentioned flat test piece on a flat surface, press one of the four corners of the test piece, and measure the maximum distance from the flat surface using the gap gauge or caliper. . Each of the four corners was pressed and the average value of the obtained warp values was determined. The smaller the warp value, the better.
(Surface gloss)
The surface gloss of a flat test piece molded under the same conditions as the warp was measured. Measurement was performed at a reflection angle of 60 ° using a mini gloss master manufactured by ERICHSEN. Relative value with respect to 50% of standard plate. The higher the surface gloss value, the better.
(Ash content)
The ash content of the polyester resin composition derived from the inorganic material was measured according to JIS K 7052.
(Production Example 1)
DMT (dimethyl terephthalate) in a reactor, 76 parts by weight of propylene glycol, 0.003 parts by weight of AO60 (a hindered phenol stabilizer of Asahi Denka Co., Ltd.) and 0.00025 parts by weight of 100 parts by weight of DMT Ti (OBu)_FourAnd stirred at a reaction temperature of about 150 to 200 ° C. to transesterify DMT and propylene glycol. Then 0.00025 parts by weight of Sb₂O_ThreeThen, melt polycondensation was performed at a reaction temperature of 270 to 280 ° C. under reduced pressure (0.8 to 5.0 torr) to obtain a polypropylene terephthalate (PPT) resin.
(Production Example 2)
Ion exchange water and a layered compound were mixed. Subsequently, it processed by adding a polyether compound or a silane type compound, and continuing mixing for 15 to 60 minutes. Thereafter, it was pulverized to obtain treated clay (layered compounds A-1 to A-4). Table 1 shows the weight ratio of the raw materials used in the production examples.
[0062]
[Table 1]

(Examples 1-7)
PET having a weight ratio shown in Table 2, the layered compound (A-1 to A-4) obtained in Production Example 2, and the epoxy compound (C-1 to C-2) were manufactured by a twin screw extruder (manufactured by Nippon Steel Co., Ltd.). The polyester resin composition was obtained and evaluated by melt-kneading at a set temperature of 230 to 260 ° C. using TEX44). The results are shown in Table 2.
(Comparative Examples 1-3)
PET, ME100, the layered compound (A-1) obtained in Production Example 2 and the epoxy compound (C-1) in the weight ratio shown in Table 2 were melt-kneaded and evaluated in the same manner as in Example 1. The results are shown in Table 2.
[0063]
[Table 2]

From Table 2, the composition obtained by biaxial extrusion of ME100 and PET resin and kneading is good in thermal stability, but since ME100 is not finely dispersed in the form of flakes, the bending characteristics are not improved, and a flat plate shape The molded product was deformed such that warpage and surface gloss could not be measured. In the system using the layered compound obtained in Production Example 2, the initial physical properties are excellent, but the workability is unstable because the viscosity decreases after melt residence, and the strength after residence and after high temperature and high humidity treatment A decline occurred. Moreover, the composition obtained by adding the epoxy compound to the PET resin increased in viscosity by being held in a molten state, and the molding processability deteriorated. That is, it can be seen that a resin composition having an excellent balance of physical properties can be obtained only by blending a PET resin with a layered compound treated with a polyether compound and a compound having an epoxy group.
(Examples 8 to 10)
The same as in Example 1 except that the PBT having the weight ratio shown in Table 3, the layered compounds (A-1, A-3) obtained in Production Example 2 and the epoxy compound (C-1) were set at a set temperature of 220 to 240 ° C. A polyester resin composition was obtained by melt kneading and evaluated. The results are shown in Table 3.
(Comparative Examples 4-6)
PBT, ME100, the layered compound (A-1) obtained in Production Example 2 and the epoxy compound (C-1) in the weight ratio shown in Table 3 were melt-kneaded and evaluated in the same manner as in Example 8. The results are shown in Table 3.
[0064]
[Table 3]

From Table 3, the composition obtained by biaxial extrusion of ME100 with PBT resin and kneading (Comparative Example 4) has less change in bending strength and B method flow value after 15 minutes retention than before residence. Although the stability is good, since ME100 is not finely dispersed in the form of flakes, the bending characteristics are not improved, and the warpage of the flat molded product is not improved. In the system using the layered compound obtained in Production Example 2, the initial physical properties are excellent, but after the melt residence, the B method flow value is increased and the viscosity is lowered, so that the workability is unstable, and after the residence and The strength decreased after the high temperature and high humidity treatment. In addition, the composition obtained by adding the epoxy compound was held in a molten state, whereby the flow value of Method B was decreased, the viscosity was increased, and the molding processability was deteriorated. That is, it can be understood that a polyester resin composition having an excellent balance of physical properties can be obtained only by blending a PBT resin with a layered compound treated with a polyether compound and a compound having an epoxy group.
(Example 11)
Example 1 except that the PPT obtained in Production Example 1 having the weight ratio shown in Table 4, the layered compound (A-1) obtained in Production Example 1, and the epoxy compound (C-1) were set at a set temperature of 220 to 250 ° C. A polyester resin composition was obtained and evaluated by melt-kneading in the same manner as described above. The results are shown in Table 4.
(Comparative Examples 7-9)
The PPT and ME100 obtained in Production Example 1 having the weight ratios shown in Table 4 and the layered compound (A-1) and epoxy compound (C-1) obtained in Production Example 2 were melt-kneaded in the same manner as in Example 11 and evaluated. did. The results are shown in Table 4.
[0065]
[Table 4]

From Table 4, the composition obtained by biaxial extrusion of ME100 and PPT resin (kneading) (Comparative Example 7) has less change in bending strength and B method flow value after 15 minutes retention than before residence. Although the stability is good, since ME100 is not finely dispersed in the form of flakes, the bending characteristics are not improved, and the warpage of the flat molded product is not improved. In the system using the layered compound obtained in Production Example 2, the initial physical properties are excellent, but after the melt residence, the B method flow value is increased and the viscosity is lowered, so that the workability is unstable, and after the residence and The strength decreased after the high temperature and high humidity treatment. In addition, the composition obtained by adding the epoxy compound was held in a molten state, whereby the flow value of Method B was decreased, the viscosity was increased, and the molding processability was deteriorated. That is, it can be seen that a polyester resin composition having an excellent balance of physical properties can be obtained only by blending a PPT resin with a layered compound treated with a polyether compound and a compound having an epoxy group.
[0066]
【The invention's effect】
As described above in detail, if the layered compound in the resin composition containing the thermoplastic polyester resin, the layered compound, and the epoxy compound satisfies at least one of the following conditions (a) to (c), the thermal stability is improved. It is possible to provide a resin molded product that is good and improved mechanical properties are maintained even after melt retention, and in addition, the warpage is improved and the surface appearance is good.
(A) Of the layered compounds in the polyester resin composition, the ratio of the layered compounds having an equivalent area circle diameter [D] of 3000 mm or less is 20% or more.
(B) The average value of the equivalent area circle diameter [D] of the layered compound in the polyester resin composition is 5000 mm or less.
(C) The [N] value is 30 or more, where the [N] value is an area of the resin composition of 100 μm.²To be defined as the number of particles per unit ratio of the layered compound present therein.

Claims (6)

A polyester resin composition comprising a thermoplastic polyester resin, a layered compound treated with a polyether compound, and a compound having an epoxy group, wherein the layered compound satisfies at least one of the following conditions (a) to (c): It meets,
The amount of the layered compound treated with the polyether compound is 0.1 to 150 parts by weight, and the amount of the compound having an epoxy group is 0.01 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin. A polyester resin composition.
(A) Of the layered compounds in the polyester resin composition, the proportion of the layered compounds having an equivalent area circle diameter [D] of 3000 mm or less is 20% or more. (B) The equivalent of the layered compound in the polyester resin composition. (C) The [N] value is 30 or more, where the [N] value is present in the area of 100 μm ² of the resin composition. Be defined as the number of particles per unit ratio of the compound   The polyester resin composition according to claim 1, wherein an average layer thickness of the layered compound is 500 mm or less.   The polyester resin composition according to claim 1 or 2, wherein the maximum thickness of the layered compound is 2000 mm or less.   The polyester resin composition according to claim 1, 2 or 3, wherein the layered compound in the resin composition has an average aspect ratio (ratio of layer length / layer thickness) of 10 to 300.   The polyester resin composition according to claim 1, 2, 3, or 4, wherein the compound containing an epoxy group does not have an ester bond.   The polyester resin composition according to claim 1, 2, 3, 4 or 5, wherein the layered compound is a layered silicate.